Non-FC Redox Electron Transfer

Since we are concerned with the Arrenhius activation energy under equilibrium conditions, a further correction should be made for the TAS change with the system in equilibrium under standard conditions, i.e., considering the relative standard entropies for for Fe2+, Fe3+ equal to -137.7 and -315.9 J/mole-K,190 a difference of -178.2 J/mole-K. The 

We should bear in mind that chemical processes in liquid media193 (which should include at least some electrochemical processes) may follow the classical Berthoud-Hinshelwood expression for the reaction rate, in which internal classical vibrational modes reduce the potential energy of activation U0 by a term involving some effective number s of classical oscillators per molecule to give EAm i.e., Eajt = U0- skT.194,195 This will show an temperature-dependent Emt, which requires further study. 

Assuming trikisoctahedral ions with average effective radii of 4.0 A, that of the inner shell (Section IV-9) in collisions with single active water molecules (radius 1.4 A), a collision frequency (Section II-8) of 

8 x 1013 s 1 is obtained. Assuming an effective reaction layer thickness of twice the mean second trikisoctahedron shell radius, i.e., 

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